【作者】 曹学锋；

【导师】 胡岳华；

【作者基本信息】 中南大学 ， 矿物加工， 2003， 博士

【摘要】 本文的研究内容主要包括以下五个方面：一水硬铝石型铝土矿主要脉石矿物的性质与捕收剂的设计、铝硅酸盐矿物捕收剂的合成、合成捕收剂的浮选性能、合成药剂对铝硅酸盐矿物的作用机理和合成胺类化合物的结构—性能的关系。 1．铝硅酸盐矿物（高岭石、叶蜡石和伊利石）均是由硅氧四面体和铝氧八面体所构成；矿物破碎时，（001）晶面解理完全，成为晶体的层面，由于晶格类质取代而荷永久负电荷，（110）面和（010）面解理不完全，成为晶体的端面，表面荷电随pH值的变化而变化；从矿物破碎时断裂键数分析知铝硅酸盐矿物的可浮性为叶蜡石＞高岭石＞伊利石；强化高岭石的捕收是铝硅酸盐矿物捕收剂设计的重点；从浮选药剂的基本构成出发，结合高岭石晶体的原子态密度图分析和铝硅酸盐矿物的表面荷电现象以及亲水—疏水平衡设计出含N型阳离子捕收剂，其极性基是：-NHCH₂CH₂CH₂NH₂、-O-CH₂CH₂CH₂NH₂和-N（CH₃）₂，非极性基是：n-C₁₂H₂₅-，n-C₁₄H₂₉-，n-C₁₆H₃₃-，n-C₁₈H₃₇-。 2．采用脂肪胺或脂肪醇对丙烯腈的亲核加成，再在金属钠与乙醇存在条件下还原而成合成了N-烷基-1，3一丙二胺类化合物四种、烷基丙基醚胺类化合物四种，采用脂肪胺的还原烷基化反应制备了N，N-二甲基-烷基胺类化合物两种，并采用高效液相色谱监测等手段，完备了合成条件，简化了实验方法，较高产率的合成了设计产品。 3．选用合成的十种捕收剂，系统地考察了它们对铝硅酸盐矿物的浮选性能，并与十二胺相比较，得知：多胺类化合物捕收铝硅酸盐矿物的顺序是叶蜡石＞高岭石＞伊利石，总体上是对高岭石和叶蜡石的捕收能力较强，对伊利石的捕收能力稍弱，但仍远强于十二胺，特别是N-十二烷基-1，3-丙二胺(DN₁₂)在广泛的pH值的范围（pH4～10）对高岭石和叶蜡石具有极强的捕收能力，捕收高岭石的能力超过了对叶蜡石的捕收，对伊利石的捕收能力与十二胺相比也大大提高，同DN系列药剂，浮选高岭石、叶蜡石和伊利石，随药剂分子碳数增加浮选性能变差；醚胺类化合物捕收铝硅酸盐矿物的顺序是叶蜡石＞高岭石＞伊利石，总体上是对叶蜡石的捕收效果好，对高岭石和博士论文摘要伊利石的捕收能力较弱，与十二胺相比，捕收铝硅酸盐矿物的能力略有提高，同ON系列药剂，浮选高岭石、叶蜡石和伊利石，随药剂分子碳数增加浮选性能变好;叔胺类化合物捕收铝硅酸盐矿物的顺序是叶蜡石>高岭石>伊利石，总体上是在酸性条件下捕收铝硅酸盐矿物较好，在碱性条件下捕收差，与十二胺相比，在微酸性和中性条件下浮选铝硅酸盐的性能得到了提高，同DRN系列药剂，浮选高岭石、叶蜡石和伊利石，随药剂分子碳数增加浮选性能变强。因此，浮选铝硅酸盐矿物，DN系列>DRN系列>0N系列。 4.利用动电位、红外光谱测试以及矿物的溶液化学分析，探讨了合成胺类捕收剂与铝硅酸盐矿物的作用原理:三类合成药剂均能显著改变铝硅酸盐矿物表面的乙一电位，说明合成胺类捕收剂与铝硅矿物发生了静电吸附作用，这种乙一电位改变是DN系列>DRN系列>0N系列;药剂与矿物作用后的红外图谱也证实了胺类捕收剂与铝硅矿物主要是发生静电物理吸附，DN系列和ON系列还能与铝硅矿物发生氢键作用;矿物的溶解平衡对药剂与矿物的吸附作用起着显著的影响，结合矿物的溶液化学行为和矿物的表面电性可以解释胺类捕收剂的浮选行为。 5.运用浮选剂的极性基基团电负性、极性基大小、浮选剂特性指数、亲水一疏水平衡值、分配系数和药剂分子、离子的量化参数以及药剂的溶液化学的计算，探讨了铝硅酸盐矿物的捕收剂的结构一性能的关系，结果表明:亲固原子品N上引入不同基团，药剂的性能将发生很大的改变，非极性基团的引入，增大了极性基的基团电负性，加强了药剂的亲固能力，但减少了药剂的起泡性和可溶性，促进了药剂在碱性条件下缔合现象发生，极性基团的引入，增多了药剂的吸附活性点，也增加了药剂的起泡性和可溶性，同时，也增大了药剂的极性基大小，增强了药剂的选择性，并减少了药剂在碱性条件下缔合现象发生，更促进了药剂与矿物的氢键的作用，从而提高药剂的捕收性能:量化计算结果表明合成的十种药剂均易形成阳离子化合物，对DN系列和ON系列，离子化使供电活性也得到了大大提高，氢键作用能力增强，有利于浮选铝硅矿物，对DRN系列，离子化使亲固原子的净电荷明显减少，静电作用能力变强，但DRN系列阳离子的氢键作用能力弱，总体捕收效果不佳;药剂的溶液化学计算进一步证实了药剂的浮选性能。更多还原

【Abstract】 The studies that relate to the anime-collectors of Al-Silicate minerals involve in the following : character of the main gangues of bauxite and design for the collectors, synthesizing, the flotation property , the adsorption mechanism and the structure-activity relationship of the collectors.Firstly, the kaolinite , pyrophyllite and illite comprise (Si, O) tetrahedron and (Al, O) octahedron. When minerals , it’s (001) cleavages completely and forms bedding plane of crystal , which carries aptotic electronegative , but it’s (110) and (010) cleavage incompletely and form end faces of crystal , which carries alterable electric charge that alter with pH . By counting breaked bond , the floatability is pyrophyllite >kaolinite>illite .So it is the point of exertion to catch kaolinite . From the basic structure model of collector and characteristic of Al-Silicate minerals , the collectors of Al-Silicate minerals are designed , the polar groups of which are -NHCH2CH2CH2NH2 , -0-CH2CH2CH2 Mi and -N (CEO 2 , and the no- polar groups of which are n-C12H25- n-C14H29,n-C16H33-,n-C18H37- .Secondly, the N- alkyl-l,3- diaminopropanes and the aether-alkyl-propyl- amines are made by the following reactions :RNH2+H2C=CH-CN→RNH2 CH2 CH2CN RNHCH2 CH2CN Na+c^OH RNH CH2 CH2 CH2 NH2 R= n-C12H25-, n-CnH29- n-C16H33; n-C18H37- .and the aether-alkyl-propyl- amines are made by the following reactions :ROH+H2C=CH-CN→RO CH2 CH2CN ROCH2 CH2CN WRO CH2 CH2 CH2 NH2R= n-C12H25- n- CMH29- n-C16H33 n-C18H37. and the N,N- dimethyl-alkyl-amines are made by the following reactions :RNH2+2HCHO HCOOH RN(CH3)2+CO2R= n-Ci2H25-, n-CHH29- .Thirdly, three pure minerals, the kaolinite , pyrophyllite and illite, are adopted for investigating the flotation properties of the synthesized reagents. TheVI__________________________________________________________________________________abstractresults of the flotation indicate that: Catching the aluminum silicate minerals, the synthesized reagents are better than the DDA. To diamines, the order of catching aluminum silicate minerals is the pyrophyllite >the kaolinite >the illite. The longer of carbon chain of the DNs, the smaller caching ability to aluminum silicate minerals. To aether-amines and to tertiary amines, the order of catching aluminum silicate minerals is the pyrophyllite >the kaolinite >the illite, and the longer of carbon chain of them, the stronger catching ability to aluminum silicate minerals. The order of catching aluminum silicate minerals is the DNs >the DRNs >the ONs. The DNi2 is the best of the synthesized reagents, which has strong caching ability to the kaolinite and pyrophyllite in wide pH (4--10).The catching mechanism of the synthesized reagents was confirmed by the measurements of zeta potential, IR spectrum and solution chemistry of aluminum silicate minerals. The synthesized reagents can adsorb on the mineral surface and change the zeta potential of aluminum silicate minerals .The IR spectrums approve that the action is electrostatic adsorption mainly and go with hydrogen bond in part. It is explained the floatation action that the synthesized reagents catch the aluminum silicate minerals by combing solution chemistry of aluminum silicate minerals and the surface electrical property.The structure-activity relationships of the collectors of the aluminum silicate minerals are discussed by the calculation of radical electro-negativity, radical size, reagent specific exponent, hydrophilic lipophilic balance, partition ratio, quantum chemistry parameters of molecule and cation , and solution chemistry of the synthesized reagents. The conclusions are following: with the no-polar groups on N of reagents increasing, the radical electro-negativity and the solid -philic energy of the reagents increase, but foamability and dissolubility of the reagents decrease, with the polar groups on N of reagents increasing, the adsorbing active points, foamability , dissolubility and radical size of the reagents increase. The selectivity and catching ability of the更多还原